Bruns Jörn, Podewitz Maren, Liedl Klaus R, Janka Oliver, Pöttgen Rainer, Huppertz Hubert
Leopold-Franzens-Universität Innsbruck, Institut für Allgemeine, Anorganische und Theoretische Chemie, Innrain 80-82, 6020, Innsbruck, Austria.
Westfälische Wilhelms-Universität Münster, Institut für Anorganische und Analytische Chemie, Corrensstrasse 30, 48149, Münster, Germany.
Angew Chem Int Ed Engl. 2018 Jul 20;57(30):9548-9552. doi: 10.1002/anie.201803395. Epub 2018 May 16.
Borosulfates are an ever-expanding class of compounds and the extent of their properties is still elusive. Herein, the first two copper borosulfates Cu[B (SO ) ] and Cu[B(SO ) (HSO )] are presented, which are structurally related but show different dimensionalities in their substructure: While Cu[B (SO ) ] reveals an anionic chain, ∞1 [B(SO ) ] , with both a twisted and a unique chair conformation of the B(SO ) B subunits, Cu[B(SO ) (HSO )] reveals isolated [B (SO ) (HSO ) ] anions showing exclusively a twisted conformation. The complex anion can figuratively be obtained as a cut-out from the anionic chain by protons. Comparative DFT calculations based on magnetochemical measurements complement the experimental studies. Calculation of the pK values of the two conformers of the [B (SO ) (HSO ) ] anion revealed them to be more similar to silicic than to sulfuric acid, highlighting the close relationship to silicates.
硼硫酸盐是一类不断扩展的化合物，其性质范围仍不明确。本文报道了前两种铜硼硫酸盐Cu[B(SO₄)₂]和Cu[B(SO₄)(HSO₄)]，它们在结构上相关，但在亚结构中显示出不同的维度：虽然Cu[B(SO₄)₂]揭示了一个阴离子链∞¹[B(SO₄)₂]²⁻，其中B(SO₄)₂亚基具有扭曲和独特的椅式构象，但Cu[B(SO₄)(HSO₄)]揭示了孤立的[B(SO₄)(HSO₄)]⁻阴离子，仅显示扭曲构象。复合阴离子可以形象地看作是质子从阴离子链上切下的部分。基于磁化学测量的比较密度泛函理论计算补充了实验研究。[B(SO₄)(HSO₄)]⁻阴离子两种构象的pKₐ值计算表明，它们与硅酸的相似性高于硫酸，突出了与硅酸盐的密切关系。
